Cofactor-independent, photoenzymatic, reductions with water mediated by rGQDs

Research Square (Research Square), Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 17, 2025

Enzymatic reductions catalyzed by reductases, such as aldo/ketoreductases (AKRs), imine and ene reductases generally depend on the regeneration of nicotinamide cofactors for industrial viability. This usually involves addition a cosubstrate second enzyme, dehydrogenase, e.g. glucose / dehydrogenase. For commercial viability it would be more interesting to use water sacrificial supply necessary hydrogen atoms. is possible using photocatalytic methods involving precious metal, Rh Ru, complexes electron mediators. A problem associated with photobiocatalysis in general weak penetration ultraviolet or visible light biological systems. Here we report unprecedented near infrared (NIR) combination hybrid photoenzyme based IR responsive reductive graphene quantum dots (rGQDs) that are non-toxic AKRs. We envisaged immobilization AKR close proximity rGQDs could enable direct transfer atoms from prochiral ketone substrate without requiring cofactor. To test this hypothesis, immobilized surface cross-linked AKR. The resulting rGQD/AKR photobiocatalyst mediated synthesis pharmaceutical intermediate, (R)-1-[3,5-bis(trifluoromethyl)-phenyl] ethanol ((R)-3,5-BTPE) corresponding ketone, 82% yield > 99.99% ee under 50 mW·cm^{− 2} illumination. work opens new avenues create artificial photoenzymes simplify in vitro biocatalysis coupling renewable solar energy sustainable chemical production. Since accounts about half entire spectrum its efficient utilization crucial applications sunlight. have demonstrated our can effectively utilize catalyze enzymatic reduction ketone. these photobiocatalysts insoluble solids they readily recovered, recycled potentially employed continuous flow operation.

Language: Английский

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“Excited” Class I Aldolases: EDA Complex Mediated Photo-biocatalytic Enantioselective β-Alkylation of Enals

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 2531 - 2539

Published: Jan. 27, 2025

Language: Английский

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Enzymatic Valorization of Fatty Acids in Oleochemical Synthesis

European Journal of Lipid Science and Technology, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 18, 2025

ABSTRACT Fatty acids derived from renewable resources, such as vegetable oils, serve essential feedstocks in various industries, including surfactants, cosmetics, lubricants, and polymers. Although current industrial applications of fatty are mainly centered around carboxylate group transformations, recent advancements biocatalysis have opened new possibilities for converting into valuable chemical building blocks. This contribution critically assesses novel biocatalytic transformations acids, hydroxylation the alkyl chain, epoxidation C═C double bonds, reduction group, decarboxylation. These reactions hold great potential producing important intermediates synthesis. Practical Application : The enzymatic valorization offers transformative sustainable oleochemical synthesis, presenting practical across industries. Hydroxylated epoxidized promising precursors production polyesters, bio‐based surfactants. Sophorolipids, hydroxylated gaining attraction biosurfactants with detergents cosmetics. Epoxidized eco‐friendly adhesives, coatings, Furthermore, decarboxylation yield alkanes, viable biofuels, whereas reductions carboxyl groups enable selective synthesis aldehydes alcohols fragrances pharmaceutical intermediates. scalability these combined their mild operational conditions high specificity, can substantially reduce environmental impact costs. highlight a pivotal technology advancing industry toward practices.

Language: Английский

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Biocatalytic oxyfunctionalization of unsaturated fatty acids to oxygenated chemicals via hydroxy fatty acids

Biotechnology Advances, Journal Year: 2024, Volume and Issue: unknown, P. 108510 - 108510

Published: Dec. 1, 2024

Language: Английский

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